Determinação de dados de equilíbrio líquido-vapor a altas pressões para sistemas de hidrocarbonetos assimétricos

Crude oil is a complex liquid mixture of organic and inorganic compounds that are dominated by hydrocarbons. It is a mixture of alkanes from the simplest to more complex aromatic compounds that are present derivatives such as gasoline, diesel, alcohol, kerosene, naphtha, etc.. These derivatives are extracted from any oil, however, only with a very high quality, in other words, when the content of hydrocarbons of low molecular weight is high means that production of these compounds is feasible. The American Petroleum Institute (API) developed a classification system for the various types of oil. In Brazil, the quality of most of the oil taken from wells is very low, so it is necessary to generate new technology to develop best practices for refining in order to produce petroleum products of higher commercial value. Therefore, it is necessary to study the thermodynamic equilibrium properties of its derivative compounds of interest. This dissertation aims to determine vapor-liquid equilibrium (VLE) data for the systems Phenilcyclohexane - CO2, and Cyclohexane - Phenilcyclohexane - CO2 at high pressure and temperatures between 30 to 70oC. Furthermore, comparisons between measured VLE experimental data from this work and from the literature in relation to the Peng- Robinson molecular thermodynamic model, using a simulation program SPECS IVCSEP v5.60 and two adjustable interaction parameters, have been performed for modeling and simulation purposes. Finally, the developed apparatus for determination of phase equilibrium data at high pressures is presented

Use of Primary Sludge from Pulp and Paper Mills for Nanocomposites

Cellulose nanocrystals have been evaluated as reinforcement material in polymeric matrices due to their potential to improve the mechanical, optical, and dielectric properties of these matrixes. This work describes how high pressure defibrillation and chemical purification affect the sludge fiber morphology from micro to nanoscale. Microscopy techniques and X-ray diffraction were used to study the structure and properties of the prepared nanofibers and composites. Microscopic studies showed that the used individualization processes lead to a unique morphology of interconnected web-like structure of sludge fibers. The nanofibers are bundles of cellulose fibers having widths (5 to 30 nm) and estimated lengths of several micrometers.

Obtenção de Propriedades Físico-Químicas de Misturas de Hidrocarbonetos em Baixa e Alta Pressão Visando a Caracterização e a Modelagem

The composition of petroleum may change from well to well and its resulting characteristics influence significantly the refine products. Therefore, it is important to characterize the oil in order to know its properties and send it adequately for processing. Since petroleum is a multicomponent mixture, the use of synthetic mixtures that are representative of oil fractions provides a better understand of the real mixture behavior. One way for characterization is usually obtained through correlation of physico-chemical properties of easy measurement, such as density, specific gravity, viscosity, and refractive index. In this work new measurements were obtained for density, specific gravity, viscosity, and refractive index of the following binary mixtures: n-heptane + hexadecane, cyclohexane + hexadecane, and benzene + hexadecane. These measurements were accomplished at low pressure and temperatures in the range 288.15 K to 310.95 K. These data were applied in the development of a new method of oil characterization. Furthermore, a series of measurements of density at high pressure and temperature of the binary mixture cyclohexane + n-hexadecane were performed. The ranges of pressure and temperature were 6.895 to 62.053 MPa and 318.15 to 413.15 K, respectively. Based on these experimental data of compressed liquid mixtures, a thermodynamic modeling was proposed using the Peng-Robinson equation of state (EOS). The EOS was modified with scaling of volume and a relatively reduced number of parameters were employed. The results were satisfactory demonstrating accuracy not only for density data, but also for isobaric thermal expansion and isothermal compressibility coefficients. This thesis aims to contribute in a scientific manner to the technological problem of refining heavy fractions of oil. This problem was treated in two steps, i.e., characterization and search of the processes that can produce streams with economical interest, such as solvent extraction at high pressure and temperature. In order to determine phase equilibrium data in these conditions, conceptual projects of two new experimental apparatus were developed. These devices consist of cells of variable volume together with a analytical static device. Therefore, this thesis contributed with the subject of characterization of hydrocarbons mixtures and with development of equilibrium cells operating at high pressure and temperature. These contributions are focused on the technological problem of refining heavy oil fractions

Equilíbrio líquido-líquido de sistemas aquosos com tensoativos polietoxilados: dados experimentais e modelagem

The nonionic surfactants when in aqueous solution, have the property of separating into two phases, one called diluted phase, with low concentration of surfactant, and the other one rich in surfactants called coacervate. The application of this kind of surfactant in extraction processes from aqueous solutions has been increasing over time, which implies the need for knowledge of the thermodynamic properties of these surfactants. In this study were determined the cloud point of polyethoxylated surfactants from nonilphenolpolietoxylated family (9,5 , 10 , 11, 12 and 13), the family from octilphenolpolietoxylated (10 e 11) and polyethoxylated lauryl alcohol (6 , 7, 8 and 9) varying the degree of ethoxylation. The method used to determine the cloud point was the observation of the turbidity of the solution heating to a ramp of 0.1 ° C / minute and for the pressure studies was used a cell high-pressure maximum ( 300 bar). Through the experimental data of the studied surfactants were used to the Flory - Huggins models, UNIQUAC and NRTL to describe the curves of cloud point, and it was studied the influence of NaCl concentration and pressure of the systems in the cloud point. This last parameter is important for the processes of oil recovery in which surfactant in solution are used in high pressures. While the effect of NaCl allows obtaining cloud points for temperatures closer to the room temperature, it is possible to use in processes without temperature control. The numerical method used to adjust the parameters was the Levenberg - Marquardt. For the model Flory- Huggins parameter settings were determined as enthalpy of the mixing, mixing entropy and the number of aggregations. For the UNIQUAC and NRTL models were adjusted interaction parameters aij using a quadratic dependence with temperature. The parameters obtained had good adjust to the experimental data RSMD < 0.3 %. The results showed that both, ethoxylation degree and pressure increase the cloudy points, whereas the NaCl decrease

Ativação local da rota da quinurenina por moduladores inflamatórios durante a meningite bacteriana.

Activation of the kynurenine (KYN) pathway (KP) by modulators of immune system has been observed during several neurological diseases. Here we assessed the association of chemo-/cytokine levels with the concentration of KP metabolites in cerebrospinal fluid (CSF) and plasma samples from patients with bacterial meningitis (BM). All samples were collected from 42 patients diagnosed with acute bacterial meningitis (ABM), aseptic meningitis, tuberculous meningitis and patients without infection neurological disorders. CSF and plasma concentration of metabolites from the KP was assessed by high pressure liquid chromatography (HPLC) and cytokines and chemokines by Bio-plex 200 suspension array system. Concentrations of the KP metabolites KYN and kynurenic acid (KYNA) were significantly higher in CSF of patients with ABM compared to other groups. Tryptophan (TRP), anthranilic acid (AA), 3-hydroxykynurenine (3HK) and 3-hydroxyanthranilic acid (3HAA) did not show statistical significance, although some of them presented a good accumulation during ABM. The expression of TNF-alpha, IL-6, IL-1beta, IFN-gamma, IL-10, IL-1 receptor antagonist (IL-1Ra), MIP-1alpha, MIP-1beta, MCP-1 and G-CSF was about 100-fold higher in CSF from ABM patients than other infected groups. In all CSF and plasma samples, the concentration of IL-2, IL-12(p70), IL-4, IL-8 and GM-CSF was not significant. ABM still showed significant concentrations of IL-6, IL-10, IL-1Ra and MCP-1 in plasma samples. Based on the comparison of KP metabolites concentrations between plasma and CSF samples we conclude that the activation of the tryptophan pathway upon BM occurs within the brain. This increase in KP metabolites is most due to activation of the KP by molecules as IFN-gamma and TNF-alpha in response to infection.

Radial Plasma Dynamic in Sequential Pinches

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Estudo da influência do biodiesel de mamona como aditivo antioxidante para o biodiesel de girassol e soja

Biodiesel is a fuel made up by mono-alkyl-esters of long chain fatty acids, derived from vegetable oils or animal fat. This fuel can be used in compression ignition engines for automotive propulsion or energy generation, as a partial or total substitute of fossil diesel fuel. Biodiesel can be processed from different mechanisms. Transesterification is the most common process for obtaining biodiesel, in which an ester compound reacts with an alcohol to form a new ester and a new alcohol. These reactions are normally catalyzed by the addition of an acid or a base. Initially sunflower, castor and soybean oil physicochemical properties are determined according to standard test methods, to evaluate if they had favorable conditions for use as raw material in the transesterification reaction. Sunflower, castor and soybean biodiesel were obtained by the methylic transesterification route in the presence of KOH and presented a yield above 93% m/m. The sunflower/castor and soybean/castor blends were studied with the aim of evaluating the thermal and oxidative stability of the biofuels. The biodiesel and blends were characterized by acid value, iodine value, density, flash point, sulfur content, and content of methanol and esters by gas chromatography (GC). Also studies of thermal and oxidative stability by Thermogravimetry (TG), Differential Scanning Calorimetry High Pressure (P-DSC) and dynamic method exothermic and Rancimat were carried out. Biodiesel sunflower and soybean are presented according to the specifications established by the Resolution ANP no 7/2008. Biodiesel from castor oil, as expected, showed a high density and kinematic viscosity. For the blends studied, the concentration of castor biodiesel to increased the density, kinematic viscosity and flash point. The addition of castor biodiesel as antioxidant in sunflower and soybean biodiesels is promising, for a significant improvement in resistance to autoxidation and therefore on its oxidative stability. The blends showed that compliance with the requirements of the ANP have been included in the range of 20-40%. This form may be used as a partial substitute of fossil diesel

Baroreflex control of heart rate in the broad-nosed caiman Caiman latirostris is temperature dependent

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Análise quantitativa e molecular de hemoglobina fetal em indivíduos da população brasileira

A hemoglobina fetal - Hb F, formada por duas cadeias gama e duas cadeias alfa, é característica do período fetal do desenvolvimento, tendo sua síntese diminuída no período pós-natal. em algumas alterações hereditárias, a Hb F permanece aumentada, como nas delta-beta talassemia, beta talassemia e persistência hereditária de Hb F (PHHF). A síntese da globina gama também pode ser estimulada por fatores externos como leucemias, transplantes de medula óssea, induções químicas, dentre outros. Através da observação de Hb F aumentada em doadores de sangue por procedimentos eletroforéticos objetivou-se avaliar a quantidade de Hb F em amostras de sangue de candidatos à doação, visando estabelecer seus limites de normalidade na população de São José do Rio Preto e região, por meio de desnaturação alcalina e cromatografia líquida de alta pressão (HPLC), comparar as metodologias aplicadas e, nos indivíduos com Hb F aumentada, realizar estudos moleculares para identificar as mutações que alteram a expressão dos genes gama. Foram analisadas 208 amostras de sangue, sendo 119 de candidatos à doação e 89 de indivíduos sem sintomas de anemia ou achados hematológicos e com Hb F aumentada como grupo comparativo. Das 119 amostras de candidatos à doação, 110 foram utilizadas para traçar o perfil de normalidade de Hb F, comparando-se as metodologias de desnaturação alcalina e HPLC, onde se obteve a média de 1,48% e de 0,6%, respectivamente. A análise estatística por regressão linear mostrou diferença significativa na comparação entre as duas metodologias aplicadas, sendo a HPLC mais precisa para a quantificação de Hb F. Foram observados nos testes de rastreamento de hemoglobinas anormais nestas 110 amostras de sangue: 16,4% de alfa talassemia, 0,9% com Hb F aumentada, 0,9% com beta talassemia e 0,9% com hemoglobina variante de cadeia delta. Os outros nove doadores de sangue apresentaram Hb F acima de 10% em eletroforese e observou-se média de 32,28% para desnaturação alcalina e de 26,4% para HPLC. As análises moleculares por PCR-ASO foram realizadas na tentativa de se identificar um defeito genético que pudesse explicar o aumento de Hb F, pelo rastreamento de 16 mutações que originam talassemias do tipo beta. Encontraram-se 5,3% de heterozigotos para mutação CD6-A e 1,75% para as mutações CD 39, IVS1:6, -87 e IVS2:654, todas em heterozigose. Os resultados encontrados neste estudo evidenciam a necessidade de melhor caracterização dos perfis de hemoglobina obtidos pelos métodos clássicos e a importância de sua caracterização molecular.

Deformational evolution of a Cretaceous subduction complex: Elephant Island, South Shetland Islands, Antarctica

New structural data from Elephant Island and adjacent islands are presented with the objective to improve the understanding of subduction kinematics in the area northeast of the Antarctic Peninsula. on the island, a first deformation phase, D-1, produced a strong SL fabric with steep stretching and mineral lineations, partly defined by relatively high pressure minerals, such as crossite and glaucophane. D-1 is interpreted to record southward subduction along an E-W trench with respect to the present position of the island. A second phase, D-2, led to intense folding with steep E-W-trending axial surfaces. The local presence of sinistral C'-type sheer bands related to this phase and the oblique inclination of the L-2 stretching lineations are the main arguments to interpret this phase as representing oblique sinistral transpressive shear along steep, approximately E-W-trending shear zones, with the northern (Pacific) block going down with respect to the southern (Antarctic Peninsula) block. The sinistral strike-slip component may represent a trench-linked strike-slip movement as a consequence of oblique subduction. Lithostatic pressure decreased and temperature increased to peak values during D-2, interpreted to represent the collision of thickened oceanic crust with the active continental margin. The last deformation phase, D-3, is characterised by post-metamorphic kink bands, partially forming conjugate sets consistent with E-W shortening and N-S extension. The rock units that underlie the island probably rotated during D-3, in Cenozoic times, together with the trench, from an NE-SW to the present ENE-WSW position, during the progressive opening of the Scotia Sea. The similarity between the strain orientation of D-3 and that of the sinistral NE-SW Shackleton Fracture Zone is consistent with this interpretation. (C) 2000 Elsevier B.V. B.V. All rights reserved.

Relics of eclogite facies assemblages in the Ceara Central Domain, NW Borborema Province, NE Brazil: Implications for the assembly of West Gondwana

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Occurrence and geochemistry of metamafic rocks from the Forquilha Eclogite Zone, central Ceara (NE Brazil): geodynamic implications

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Construção de uma célula-autoclave para medidas eletroquímicas a altas temperaturas

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Efeito de espalhante-adesivo na eficiência dos acaricidas propargite e cyhexatin no controle do Brevipalpus phoenicis (Geijskes) (Acari: Tenuipalpidae) em citros

Embora espalhantes-adesivos sejam considerados importantes em pulverizações, existem dúvidas quanto à sua utilidade em pulverizações a alto volume quando o escorrimento é maior, como nas aplicações com equipamentos tipo pistola, para o controle de Brevipalpus phoenicis (Geijskes). Dois ensaios de campo foram conduzidos, em 1991 e 1994, em pomar de citros cv. Natal. As pulverizações foram realizadas com pulverizador tratorizado equipado com pistolas de alta pressão usando 18 l e 11 l de calda/planta, respectivamente. Efeitos dos espalhante-adesivo foi avaliado contando-se o número de ácaros antes e após a aplicação. Não se verificaram diferenças sensíveis na retenção do líquido pulverizado nas folhas de citros quando se adicionou o espalhante-adesivo à calda com propargite. Redução de até 95,6% na população do ácaro foi obsevada com o aumento na dosagem do propargite e de até 98,9% em relação de menor dosagem para o cyhexatin. Constatou-se que o espalhante-adesivo não melhorou a eficiência do cyhexatin, embora a somatória dos totais de ácaros, independentemente da dosagem e da formulação, tenha sido 50,1% menor com o uso de espalhante-adesivo.

Desempenho e composição corporal de novilhas alimentadas com dois níveis de concentrado e bagaço de cana submetidos a diferentes processos de hidrólise

O objetivo deste trabalho foi testar duas formas de hidrólise do bagaço de cana (com [17kgf/cm²]e sem [4kgf/cm²] rápida descompressão pós-hidrólise) e dois níveis de concentrado (25 e 45% MS) no desempenho e na composição corporal de novilhas em crescimento sob regime confinado durante 112 dias. Vinte e quatro novilhas Nelore e 12 Canchim foram distribuídas em delineamento de blocos casualizados em arranjo fatorial 2x2. Os resultados demonstraram que a omissão da explosão pós-hidrólise e o uso de níveis mais elevados de concentrado aumentaram o ganho de peso e o consumo de alimentos. Os resultados para ganho de peso e consumo de matéria seca, respectivamente, para tratamento sem vs com descompressão e 45 vs 25% de concentrado, foram 0,76 vs 0,67 e 0,76 vs 0,66 kg/d e 6,7 vs 5,8 e 6,8 vs 5,7 kg/dia. Entretanto, não houve diferença entre os tratamentos para conversão alimentar. Não foram observadas diferenças entre os tratamentos quanto à composição corporal determinada por meio do espaço de deutério ao final do período de confinamento, embora a taxa estimada de deposição de lipídios tenha sido maior para o tratamento sem explosão (216 vs 175 g/d) e o tratamento com 45% de concentrado (225 vs 166 g/d). Não foram observadas vantagens na descompressão rápida pós-hidrólise em alta pressão na eficiência de conversão de alimentos. Os resultados demonstram que animais alimentados com bagaço hidrolisado em níveis altos de ingestão (2,9% PV) e proporções baixas de concentrado apresentaram eficiência de utilização da dieta semelhante a dietas com níveis mais altos de concentrado.